Novel dihydropyrrolo[2,3-f] indole-diketopyrrolopyrrole semiconducting materials, and methods and uses thereof

ABSTRACT

Described herein are heterocyclic organic compounds. More specifically, described herein are compounds based on the combination of fused pyrrole structures with diketopyrrolopyrrole structures, methods for making these compounds, and uses thereof. The compounds disclosed have improved electronic, polymerization and stability properties that allow for improved material processibility and inclusion in organic semiconductor devices.

This application is a continuation of International Application No.PCT/US15/17710 filed Feb. 26, 2015, the content of which claims thebenefit of priority under 35 U.S.C. §119 of U.S. Provisional ApplicationSer. No. 61/946,004, filed on Feb. 28, 2014, the content of which isrelied upon and incorporated herein by reference in its entirety.

FIELD

Described herein are compositions including heterocyclic organiccompounds. More specifically, described herein are fusedpyrrole-containing compounds in combination with diketopyrrolopyrrolecompounds, methods for making them, and uses thereof.

TECHNICAL BACKGROUND

Highly conjugated organic materials, due to their interesting electronicand optoelectronic properties, are being investigated for use in avariety of applications, including organic semiconductors (OSCs), fieldeffect transistors (FETs), thin-film transistors (TFTs), organiclight-emitting diodes (OLEDs), electro-optic (EO) applications, asconductive materials, as two photon mixing materials, as organicsemiconductors, and as non-linear optical (NLO) materials.

In particular, OSCs have attracted a great amount of attention in theresearch community due to their advantages over inorganicsemiconductors, including easy processing, high mechanical flexibility,low cost production, and low weights. Polycyclic aromatic compounds,such as oligothiophenes, acenes, rylenes, phthalocyanens, andpolythiophene, have been widely studied as semiconductor materials.

Among the organic p-type semiconductors, pentacene exhibits chargemobilities well above 1 cm²/V·s in organic field effect transistordevices. This number has been set up as a bench mark for new smallmolecule systems in terms of mobility requirements. However, due to thecontinuing need for improved performance and stability in semiconductorstructures, there continues to be an unmet need to develop betterperforming OSCs that have improved mobility, are structurally stable,and applicable to the large number of potential applications seen in thevarious high technology markets.

SUMMARY

Embodiments comprise a rationally designed family of compounds andpolymers comprising optionally-substituted dihydropyrroloindoles(“DHPI”), dipyrrolothiophenes or fused pyrroles (all generally referredto as “pyrrole groups” herein) bridged to optionally substituteddiketopyrrolopyrroles (“DPP”). The materials have advantages over DPPalone in that they are soluble in non-chlorinated solvents, efficientlysynthesized, and show very high mobilities in non-chlorinated solvents.Further, the compounds are relatively easy to modify and substituentscan be introduced to multiple positions which allows for fine tuningmaterial packing behaviors.

A first embodiment comprises a compound of formula:

wherein Ar is an optionally substituted aromatic or heteroaromaticgroup; k is an integer from 0 to 5 with the proviso that when k is 0,the structure results in a direct bond between the thiophene and pyrrolegroup; each X is independently NR₁, PR₁, AsR₁, Sb, O, S, Te, or Se, withthe proviso that due to conjugation, X may be bonded to one or moreadditional R₁; each Y is independently H, halo, trialkylsilane,optionally substituted C₁-C₄₀ alkyl, optionally substituted aralkyl,alkoxy, alkylthio, optionally substituted C₂-C₄₀ alkenyl, optionallysubstituted C₂-C₄₀ alkynyl, aminocarbonyl, acylamino, acyloxy, aryl,aryloxy, optionally substituted amino, carboxyalkyl, optionallysubstituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl,optionally substituted heteroaryl, optionally substituted heteroaralkyl,heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio,heteroarylthiol, optionally substituted sulfoxide, optionallysubstituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)₃, SnH₃,B(OH)₂, B(alkoxy)₂, or OTs; and each R, R₁, R₂, and R₃ is independentlyH, halo, optionally substituted C₁-C₄₀ alkyl, optionally substitutedaralkyl, alkoxy, alkylthio, optionally substituted C₂-C₄₀ alkenyl,optionally substituted C₂-C₄₀ alkynyl, aminocarbonyl, acylamino,acyloxy, optionally substituted aryl, aryloxy, optionally substitutedamino, carboxyalkyl, optionally substituted cycloalkyl, optionallysubstituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionallysubstituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionallysubstituted sulfoxide, or optionally substituted sulfone.

In some embodiments, the compound comprises 1a or 1b. In otherembodiments, the compound comprises 1c, 1d, or 1e. In still otherembodiments, the compound comprises 2. In some embodiments, X is NR₁,PR₁, AsR₁, Sb, O, S, Se, or Te; and each R, R₁, R₂, and R₃ isindependently H, halo, optionally substituted C₁-C₄₀ alkyl, optionallysubstituted aralkyl, alkoxy, alkylthio, optionally substituted C₂-C₄₀alkenyl, optionally substituted C₂-C₄₀ alkynyl, aminocarbonyl,acylamino, acyloxy, optionally substituted aryl, aryloxy, optionallysubstituted amino, carboxyalkyl, optionally substituted cycloalkyl,optionally substituted cycloalkenyl, halo, acyl, optionally substitutedheteroaryl, optionally substituted heteroaralkyl, heteroaryloxy,optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol,optionally substituted sulfoxide, or optionally substituted sulfone.

In other embodiments, each R, R₁, R₂, and R₃ is independently H, halo,optionally substituted C₁-C₂₀ alkyl, optionally substituted aralkyl,alkoxy, alkylthio, optionally substituted C₂-C₂₀ alkenyl, optionallysubstituted C₂-C₂₀ alkynyl, optionally substituted cycloalkyl,optionally substituted cycloalkenyl, halo, optionally substitutedheterocyclyl, or an optionally substituted aryl or optionallysubstituted heteroaryl from the group consisting of phenyl, thiophenyl,furanyl, pyrrolyl, imidazolyl, triazolyl, oxaxolyl, thiazolyl,pyridinyl, pyrimidinyl, triazinyl, naphthalenyl, isoquinolinyl,quinolinyl, or naphthyridinyl. In some embodiments, each R₂ isindependently H, halo, or optionally substituted C₁-C₂₀ alkyl.

In particular embodiments, it is advantageous to have at least one ormore of R, R₂, or R₃ independently be an optionally substituted C₁-C₂₀alkyl, and in particular an optionally substituted branched C₁-C₂₀alkyl. Particular embodiments may have optionally substituted C₁-C₂₀alkyl groups only on one or more R₂ groups, or alternatively only on oneor more R groups.

In some embodiments, the compound comprises 1a, 1b, 1c, 1d, 1e or 2, andthe hole reorganization energy is less than 0.75 eV, less than 0.65,less than 0.5, less than 0.4, or less than 0.35 eV. In some embodiments,the hole reorganization energy is from about 0.05 to about 0.75, about0.05 to about 0.65, about 0.05 to about 0.5, about 0.05 to about 0.04 orabout 0.05 to about 0.35 eV.

Another embodiment comprises a polymer of formula:

wherein Ar is an optionally substituted aromatic or heteroaromatic groupor conjugated group; k is an integer from 0 to 5 with the proviso thatwhen k is 0, the structure results in a direct bond between thethiophene and diindole groups; n is an integer greater than zero; each Xis independently NR₁, PR₁, AsR₁, Sb, O, S, Te, or Se, with the provisothat due to conjugation, X may be bonded to one or more additional R₁;each R, R₁, R₂, and R₃ is independently H, halo, optionally substitutedC₁-C₄₀ alkyl, optionally substituted aralkyl, alkoxy, alkylthio,optionally substituted C₂-C₄₀ alkenyl, optionally substituted C₂-C₄₀alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted aryl,aryloxy, optionally substituted amino, carboxyalkyl, optionallysubstituted cycloalkyl, optionally substituted cycloalkenyl, acyl,optionally substituted heteroaryl, optionally substituted heteroaralkyl,heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio,heteroarylthiol, optionally substituted sulfoxide, or optionallysubstituted sulfone.

In some embodiments, the compound comprises 1a′ or 1b′. In otherembodiments, the compound comprises 1c′, 1d′, or 1e′. In still otherembodiments, the compound comprises 2′. In some embodiments, for 1a′,1b′, 1c′, 1d′, 1e′, or 2′, X is NR₁, PR₁, AsR₁, Sb, 0, S, Se, or Te,with the proviso that due to conjugation, X₁ may be bonded to one ormore additional R₁; and each R, R₁, R₂, and R₃ is independently H, halo,optionally substituted C₁-C₂₀ alkyl, optionally substituted aralkyl,alkoxy, alkylthio, optionally substituted C₂-C₂₀ alkenyl, optionallysubstituted C₂-C₂₀ alkynyl, aminocarbonyl, acylamino, acyloxy,optionally substituted aryl, aryloxy, optionally substituted amino,carboxyalkyl, optionally substituted cycloalkyl, optionally substitutedcycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionallysubstituted heteroaralkyl, heteroaryloxy, optionally substitutedheterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substitutedsulfoxide, or optionally substituted sulfone.

In other embodiments, each R, R₁, R₂, and R₃ is independently H, halo,optionally substituted C₁-C₂₀ alkyl, optionally substituted aralkyl,alkoxy, alkylthio, optionally substituted C₂-C₂₀ alkenyl, optionallysubstituted C₂-C₂₀ alkynyl, optionally substituted cycloalkyl,optionally substituted cycloalkenyl, halo, optionally substitutedheterocyclyl, or an optionally substituted aryl or optionallysubstituted heteroaryl from the group consisting of phenyl, thiophenyl,furanyl, pyrrolyl, imidazolyl, triazolyl, oxaxolyl, thiazolyl,pyridinyl, pyrimidinyl, triazinyl, naphthalenyl, isoquinolinyl,quinolinyl, or naphthyridinyl. In some embodiments, each R₂ isindependently H, halo, or optionally substituted C₁-C₂₀ alkyl.

In particular embodiments, it is advantageous to have at least one ormore of R, R₂, or R₃ independently be an optionally substituted C₁-C₂₀alkyl, and in particular an optionally substituted branched C₁-C₂₀alkyl. Particular embodiments may have optionally substituted C₁-C₂₀alkyl groups only on one or more R₂ groups, or alternatively only on oneor more R groups.

In some embodiments, for 1a′, 1b′, 1c′, 1d′, 1e′, or 2′, n is an integerfrom 1 to 500 and k is an integer from 1 to 3.

Another embodiment comprises a method of synthesizing a compoundcomprising:

comprising respectively allowing one or more diindole compounds tooptionally react with a DPP compound, wherein each Y, k, X, R, R₁, R₂and R₃ is as described above.

Another embodiment comprises a method of making a compound of structure:

Comprising respectively polymerizing a compound of structure:

wherein each X, R, R₁, R₂, R₃, n, and k is as described above and each Yis independently a reactive group that allows for polymerization. Insome embodiments each Y is independently H, halo, trialkylsilaneoptionally substituted C₁-C₂₀ alkyl, optionally substituted aralkyl,alkoxy, alkylthio, optionally substituted C₂-C₂₀ alkenyl, optionallysubstituted C₂-C₄₀ alkynyl, aminocarbonyl, acylamino, acyloxy, aryl,aryloxy, optionally substituted amino, carboxyalkyl, optionallysubstituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl,optionally substituted hetero aryl, optionally substitutedheteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl,thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide,optionally substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)₃,SnH₃, B(OH)₂, B(alkoxy)₂, or OTs.

Another embodiment comprises a device comprising compound 1a, 1b, 1c,1d, 1e, or 2 or polymer 1a′, 1b′, 1c′, 1d′, 1e′, or 2′.

Additional features and advantages will be set forth in the detaileddescription which follows, and in part will be readily apparent to thoseskilled in the art from the description or recognized by practicing theembodiments as described in the written description and claims hereof,as well as in the appended drawings.

It is to be understood that both the foregoing general description andthe following detailed description are merely exemplary, and areintended to provide an overview or framework for understanding.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings are included to provide a furtherunderstanding, and are incorporated in and constitute a part of thisspecification.

FIG. 1 is a graph of a simple mobility ranking metric based on linearcombination of Neutral Dipole Moment and the inverse of theReorganization Energy. Corresponding values for this metric have to bemaximized for an optimal mobility property. Corning's previous polymeris at the Pareto Front 27 and is ranked lowest in this classification.

DETAILED DESCRIPTION

Before the present materials, articles, and/or methods are disclosed anddescribed, it is to be understood that the aspects described below arenot limited to specific compounds, synthetic methods, or uses as suchmay, of course, vary. It is also to be understood that the terminologyused herein is for the purpose of describing particular aspects only andis not intended to be limiting.

In this specification and in the claims that follow, reference will bemade to a number of terms that shall be defined to have the followingmeanings:

Throughout this specification, unless the context requires otherwise,the word “comprise,” or variations such as “comprises” or “comprising,”will be understood to imply the inclusion of a stated integer or step orgroup of integers or steps but not the exclusion of any other integer orstep or group of integers or steps.

It must be noted that, as used in the specification and the appendedclaims, the singular forms “a,” “an” and “the” include plural referentsunless the context clearly dictates otherwise.

“Optional” or “optionally” means that the subsequently described eventor circumstance can or cannot occur, and that the description includesinstances where the event or circumstance occurs and instances where itdoes not.

Ranges may be expressed herein as from “about” one particular value,and/or to “about” another particular value. When such a range isexpressed, another aspect includes from the one particular value and/orto the other particular value. Similarly, when values are expressed asapproximations, by use of the antecedent “about,” it will be understoodthat the particular value forms another aspect. It will be furtherunderstood that the endpoints of each of the ranges are significant bothin relation to the other endpoint, and independently of the otherendpoint.

The term “alkyl” refers to a monoradical branched or unbranchedsaturated hydrocarbon chain having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,12, 13, 14, 15, 16, 17, 18, 19, 20, 30, or 40 carbon atoms, in someembodiments having 2 to 20 carbon atoms and more typically having 10 to20 carbon atoms, wherein the number of carbons in the alkyl isdesignated by the range C_(a)-C_(b), where “a” is the lower limit and“b” is the upper limit. This term is exemplified by groups such asmethyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, t-butyl,n-hexyl, n-decyl, tetradecyl, and the like.

The term “substituted alkyl” refers to: (1) an alkyl group as definedabove, having 1, 2, 3, 4 or 5 substituents, typically 1 to 3substituents, selected from the group consisting of alkenyl, alkynyl,alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino,aminocarbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy,keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio, heteroarylthio,heterocyclylthio, thiol, alkylthio, aryl, aryloxy, heteroaryl,aminosulfonyl, aminocarbonylamino, heteroaryloxy, heterocyclyl,heterocyclooxy, hydroxyamino, alkoxyamino, nitro, —SO— alkyl, —SO-aryl,—SO-heteroaryl, —SO₂-alkyl, SO₂-aryl and —SO₂-heteroaryl. Unlessotherwise constrained by the definition, all substituents may optionallybe further substituted by 1, 2, or 3 substituents chosen from alkyl,carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF₃,amino, substituted amino, cyano, and —S(O)_(n)R_(SO), where R_(SO) isalkyl, aryl, or heteroaryl and n is 0, 1 or 2; or (2) an alkyl group asdefined above that is interrupted by 1-10 atoms independently chosenfrom oxygen, sulfur and NR_(a), where R_(a) is chosen from hydrogen,alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, heteroaryl andheterocyclyl. All substituents may be optionally further substituted byalkyl, alkoxy, halogen, CF₃, amino, substituted amino, cyano, or—S(O)_(n)R_(SO), in which R_(SO) is alkyl, aryl, or heteroaryl and n is0, 1 or 2; or (3) an alkyl group as defined above that has both 1, 2, 3,4 or 5 substituents as defined above and is also interrupted by 1-10atoms as defined above.

The term “alkylene” refers to a diradical of a branched or unbranchedsaturated hydrocarbon chain, having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms, typically 1-10 carbonatoms, more typically 1, 2, 3, 4, 5 or 6 carbon atoms. This term isexemplified by groups such as methylene (—CH₂—), ethylene (—CH₂CH₂—),the propylene isomers (e.g., —CH₂CH₂CH₂— and —CH(CH₃)CH₂—) and the like.

The term “substituted alkylene” refers to: (1) an alkylene group asdefined above having 1, 2, 3, 4, or 5 substituents selected from thegroup consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl,cycloalkenyl, acyl, acylamino, acyloxy, amino, aminocarbonyl,alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl,carboxy, carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio,thiol, alkylthio, aryl, aryloxy, heteroaryl, aminosulfonyl,aminocarbonylamino, heteroaryloxy, heterocyclyl, heterocyclooxy,hydroxyamino, alkoxyamino, nitro, —SO— alkyl, —SO-aryl, —SO-hetero aryl,—SO₂-alkyl, —SO₂-aryl and —SO₂-heteroaryl. Unless otherwise constrainedby the definition, all substituents may optionally be furthersubstituted by 1, 2, or 3 substituents chosen from alkyl, carboxy,carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF₃, amino,substituted amino, cyano, and —S(O)_(n)R_(SO), where R_(SO) is alkyl,aryl, or heteroaryl and n is 0, 1 or 2; or (2) an alkylene group asdefined above that is interrupted by 1-20 atoms independently chosenfrom oxygen, sulfur and NR_(a)—, where R_(a) is chosen from hydrogen,optionally substituted alkyl, cycloalkyl, cycloalkenyl, aryl, heteroaryland heterocyclyl, or groups selected from carbonyl, carboxyester,carboxyamide and sulfonyl; or (3) an alkylene group as defined abovethat has both 1, 2, 3, 4 or 5 substituents as defined above and is alsointerrupted by 1-20 atoms as defined above. Examples of substitutedalkylenes are chloromethylene (—CH(Cl)—), aminoethylene (—CH(NH₂)CH₂—),methylaminoethylene (—CH(NHMe)CH₂—), 2-carboxypropylene isomers(—CH₂CH(CO₂H)CH₂—), ethoxyethyl (—CH₂CH₂O—CH₂CH₂—),ethylmethylaminoethyl (—CH₂CH₂N(CH₃)CH₂CH₂—), and the like.

The term “aralkyl” refers to an aryl group covalently linked to analkylene group, where aryl and alkylene are defined herein. “Optionallysubstituted aralkyl” refers to an optionally substituted aryl groupcovalently linked to an optionally substituted alkylene group. Sucharalkyl groups are exemplified by benzyl, phenylethyl,3-(4-methoxyphenyl)propyl, and the like.

The term “alkoxy” refers to the group R—O—, where R is an optionallysubstituted alkyl or optionally substituted cycloalkyl, or R is a group-Q-Z, in which Q is optionally substituted alkylene and Z is optionallysubstituted alkenyl, optionally substituted alkynyl; or optionallysubstituted cycloalkenyl, where alkyl, alkenyl, alkynyl, cycloalkyl andcycloalkenyl are as defined herein. Typical alkoxy groups are optionallysubstituted alkyl-O— and include, by way of example, methoxy, ethoxy,n-propoxy, iso-propoxy, n-butoxy, tert-butoxy, sec-butoxy, n-pentoxy,n-hexoxy, 1,2-dimethylbutoxy, trifluoromethoxy, and the like.

The term “alkylthio” refers to the group R_(S)—S—, where R_(S) is as Ris defined for alkoxy.

The term “alkenyl” refers to a monoradical of a branched or unbranchedunsaturated hydrocarbon group typically having from 2 to 40 carbonatoms, more typically 2 to 20 carbon atoms and even more typically 2 to10 carbon atoms and having 1-6, typically 1, double bond (vinyl).Typical alkenyl groups include ethenyl or vinyl (—CH═CH₂), 1-propyleneor allyl (—CH₂CH═CH₂), isopropylene (—C(CH₃)═CH₂),bicyclo[2.2.1]heptene, and the like. In the event that alkenyl isattached to nitrogen, the double bond cannot be alpha to the nitrogen.

The term “substituted alkenyl” refers to an alkenyl group as definedabove having 1, 2, 3, 4 or 5 substituents, and typically 1, 2, or 3substituents, selected from the group consisting of alkyl, alkenyl,alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy,amino, aminocarbonyl, alkoxycarbonylamino, azido, cyano, halogen,hydroxy, keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio,heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy,heteroaryl, aminosulfonyl, aminocarbonylamino, heteroaryloxy,heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro, —SO—alkyl, —SO-aryl, —SO— heteroaryl, —SO₂-alkyl, SO₂-aryl and—SO₂-heteroaryl. Unless otherwise constrained by the definition, allsubstituents may optionally be further substituted by 1, 2, or 3substituents chosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl,hydroxy, alkoxy, halogen, CF₃, amino, substituted amino, cyano, and—S(O)_(n)R_(SO), where R_(SO) is alkyl, aryl, or heteroaryl and n is 0,1 or 2.

The term “alkynyl” refers to a monoradical of an unsaturatedhydrocarbon, typically having from 2 to 40 carbon atoms, more typically2 to 20 carbon atoms and even more typically 2 to 10 carbon atoms andhaving at least 1 and typically from 1-6 sites of acetylene (triplebond) unsaturation. Typical alkynyl groups include ethynyl, (—C≡CH),propargyl (or prop-1-yn-3-yl, —CH₂C≡CH), and the like. In the event thatalkynyl is attached to nitrogen, the triple bond cannot be alpha to thenitrogen.

The term “substituted alkynyl” refers to an alkynyl group as definedabove having 1, 2, 3, 4 or 5 substituents, and typically 1, 2, or 3substituents, selected from the group consisting of alkyl, alkenyl,alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy,amino, aminocarbonyl, alkoxycarbonylamino, azido, cyano, halogen,hydroxy, keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio,heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy,heteroaryl, aminosulfonyl, aminocarbonylamino, heteroaryloxy,heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro,—SO-alkyl, —SO-aryl, —SO-heteroaryl, —SO₂-alkyl, SO₂-aryl and—SO₂-heteroaryl. Unless otherwise constrained by the definition, allsubstituents may optionally be further substituted by 1, 2, or 3substituents chosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl,hydroxy, alkoxy, halogen, CF₃, amino, substituted amino, cyano, and—S(O)_(n)R_(SO), where R_(SO) is alkyl, aryl, or heteroaryl and n is 0,1 or 2.

The term “aminocarbonyl” refers to the group —C(O)NR_(N)R_(N) where eachR_(N) is independently hydrogen, alkyl, aryl, heteroaryl, heterocyclylor where both R_(N) groups are joined to form a heterocyclic group(e.g., morpholino). Unless otherwise constrained by the definition, allsubstituents may optionally be further substituted by 1-3 substituentschosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy,alkoxy, halogen, —CF₃, amino, substituted amino, cyano, and—S(O)_(n)R_(SO), where R_(SO) is alkyl, aryl, or heteroaryl and n is 0,1 or 2.

The term “acylamino” refers to the group —NR_(NCO)C(O)R where eachR_(NCO) is independently hydrogen, alkyl, aryl, heteroaryl, orheterocyclyl. Unless otherwise constrained by the definition, allsubstituents may optionally be further substituted by 1-3 substituentschosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy,alkoxy, halogen, CF₃, amino, substituted amino, cyano, and—S(O)_(n)R_(SO), where R_(SO) is alkyl, aryl, or heteroaryl and n is 0,1 or 2.

The term “acyloxy” refers to the groups —O(O)C-alkyl, —O(O)C-cycloalkyl,—O(O)C-aryl, —O(O)C-heteroaryl, and —O(O)C-heterocyclyl. Unlessotherwise constrained by the definition, all substituents may beoptionally further substituted by alkyl, carboxy, carboxyalkyl,aminocarbonyl, hydroxy, alkoxy, halogen, —CF₃, amino, substituted amino,cyano, and —S(O)_(n)R_(SO), where R_(SO) is alkyl, aryl, or heteroaryland n is 0, 1 or 2.

The term “aryl” refers to an aromatic carbocyclic group of 6 to 20carbon atoms having a single ring (e.g., phenyl) or multiple rings(e.g., biphenyl), or multiple condensed (fused) rings (e.g., naphthyl oranthryl). Typical aryls include phenyl, naphthyl and the like.

Unless otherwise constrained by the definition for the aryl substituent,such aryl groups can optionally be substituted with from 1 to 5substituents, typically 1 to 3 substituents, selected from the groupconsisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, aminocarbonyl,alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl,carboxy, carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio,thiol, alkylthio, aryl, aryloxy, heteroaryl, aminosulfonyl,aminocarbonylamino, heteroaryloxy, heterocyclyl, heterocyclooxy,hydroxyamino, alkoxyamino, nitro, —SO-alkyl, —SO-aryl, —SO— heteroaryl,—SO₂-alkyl, SO₂-aryl and —SO₂-heteroaryl. Unless otherwise constrainedby the definition, all substituents may optionally be furthersubstituted by 1-3 substituents chosen from alkyl, carboxy,carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF₃, amino,substituted amino, cyano, and —S(O)_(n)R_(SO), where R_(SO) is alkyl,aryl, or heteroaryl and n is 0, 1 or 2.

The term “aryloxy” refers to the group aryl-O— wherein the aryl group isas defined above, and includes optionally substituted aryl groups asalso defined above. The term “arylthio” refers to the group aryl-S—,where aryl is as defined as above.

The term “amino” refers to the group —NH₂.

The term “substituted amino” refers to the group —NR_(W)R_(W) where eachR_(W) is independently selected from the group consisting of hydrogen,alkyl, cycloalkyl, carboxyalkyl (for example, benzyloxycarbonyl), aryl,heteroaryl and heterocyclyl provided that both R_(W) groups are nothydrogen, or a group —Y—Z, in which Y is optionally substituted alkyleneand Z is alkenyl, cycloalkenyl, or alkynyl. Unless otherwise constrainedby the definition, all substituents may optionally be furthersubstituted by 1-3 substituents chosen from alkyl, carboxy,carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF₃, amino,substituted amino, cyano, and —S(O)_(n)R_(SO), where R_(SO) is alkyl,aryl, or heteroaryl and n is 0, 1 or 2.

The term “carboxyalkyl” refers to the groups —C(O)O-alkyl or—C(O)O-cycloalkyl, where alkyl and cycloalkyl, are as defined herein,and may be optionally further substituted by alkyl, alkenyl, alkynyl,alkoxy, halogen, CF₃, amino, substituted amino, cyano, and—S(O)_(n)R_(SO), in which R_(SO) is alkyl, aryl, or heteroaryl and n is0, 1 or 2.

The term “cycloalkyl” refers to carbocyclic groups of from 3 to 20carbon atoms having a single cyclic ring or multiple condensed rings.Such cycloalkyl groups include, by way of example, single ringstructures such as cyclopropyl, cyclobutyl, cyclopentyl, cyclooctyl, andthe like, or multiple ring structures such as adamantanyl,bicyclo[2.2.1]heptane, 1,3,3-trimethylbicyclo[2.2.1]hept-2-yl,(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl), or carbocyclic groups to whichis fused an aryl group, for example indane, and the like.

The term “cycloalkenyl” refers to carbocyclic groups of from 3 to 20carbon atoms having a single cyclic ring or multiple condensed ringswith at least one double bond in the ring structure.

The terms “substituted cycloalkyl” or “substituted cycloalkenyl” referto cycloalkyl or cycloalkenyl groups having 1, 2, 3, 4 or 5substituents, and typically 1, 2, or 3 substituents, selected from thegroup consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, aminocarbonyl,alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl,carboxy, carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio,thiol, alkylthio, aryl, aryloxy, heteroaryl, aminosulfonyl,aminocarbonylamino, heteroaryloxy, heterocyclyl, heterocyclooxy,hydroxyamino, alkoxyamino, nitro, —SO-alkyl, —SO-aryl, —SO-heteroaryl,—SO₂-alkyl, SO₂-aryl and —SO₂-heteroaryl. Unless otherwise constrainedby the definition, all substituents may optionally be furthersubstituted by 1, 2, or 3 substituents chosen from alkyl, carboxy,carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF₃, amino,substituted amino, cyano, and —S(O)_(n)R_(SO), where R_(SO) is alkyl,aryl, or heteroaryl and n is 0, 1 or 2.

The term “halogen” or “halo” refers to a fluoro, bromo, chloro, and iodosubstituent.

The term “acyl” denotes a group —C(O)R_(CO), in which R_(CO) ishydrogen, optionally substituted alkyl, optionally substitutedcycloalkyl, optionally substituted heterocyclyl, optionally substitutedaryl, and optionally substituted heteroaryl.

The term “heteroaryl” refers to a radical derived from an aromaticcyclic group (i.e., fully unsaturated) having 1, 2, 3, 4, 5, 6, 7, 8, 9,10, 11, 12, 13, 14, or 15 carbon atoms and 1, 2, 3 or 4 heteroatomsselected from oxygen, nitrogen and sulfur within at least one ring. Suchheteroaryl groups can have a single ring (e.g., pyridyl or furyl) ormultiple condensed rings (e.g., indolizinyl, benzothiazolyl, orbenzothienyl). Examples of heteroaryls include, but are not limited to,[1,2,4]oxadiazole, [1,3,4]oxadiazole, [1,2,4]thiadiazole,[1,3,4]thiadiazole, pyrrole, imidazole, pyrazole, thiophene, pyridine,pyrazine, pyrimidine, pyridazine, indolizine, isoindole, indole,indazole, purine, quinolizine, isoquinoline, quinoline, phthalazine,naphthylpyridine, quinoxaline, quinazoline, cinnoline, pteridine,carbazole, carboline, phenanthridine, acridine, phenanthroline,isothiazole, phenazine, isoxazole, phenoxazine, phenothiazine,imidazolidine, imidazoline, triazole, oxazole, thiazole, naphthyridine,and the like as well as N-oxide and N-alkoxy derivatives of nitrogencontaining heteroaryl compounds, for example pyridine-N-oxidederivatives.

Unless otherwise constrained by the definition for the heteroarylsubstituent, such heteroaryl groups can be optionally substituted with 1to 5 substituents, typically 1 to 3 substituents selected from the groupconsisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, aminocarbonyl,alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl,carboxy, carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio,thiol, alkylthio, aryl, aryloxy, heteroaryl, amino sulfonyl,aminocarbonyl amino, heteroaryloxy, heterocyclyl, heterocyclooxy,hydroxyamino, alkoxyamino, nitro, —SO— alkyl, —SO-aryl, —SO-heteroaryl,—SO₂-alkyl, SO₂-aryl and —SO₂-heteroaryl. Unless otherwise constrainedby the definition, all substituents may optionally be furthersubstituted by 1-3 substituents chosen from alkyl, carboxy,carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF₃, amino,substituted amino, cyano, and —S(O)_(n)R_(SO), where R_(SO) is alkyl,aryl, or heteroaryl and n is 0, 1 or 2.

The term “heteroaralkyl” refers to a heteroaryl group covalently linkedto an alkylene group, where heteroaryl and alkylene are defined herein.“Optionally substituted heteroaralkyl” refers to an optionallysubstituted heteroaryl group covalently linked to an optionallysubstituted alkylene group. Such heteroaralkyl groups are exemplified by3-pyridylmethyl, quinolin-8-ylethyl, 4-methoxythiazol-2-ylpropyl, andthe like.

The term “heteroaryloxy” refers to the group heteroaryl-O—.

The term “heterocyclyl” refers to a monoradical saturated or partiallyunsaturated group having a single ring or multiple condensed rings,having from 1 to 40 carbon atoms and from 1 to 10 hetero atoms,typically 1, 2, 3 or 4 heteroatoms, selected from nitrogen, sulfur,phosphorus, and/or oxygen within the ring. Heterocyclic groups can havea single ring or multiple condensed rings, and includetetrahydrofuranyl, morpholino, piperidinyl, piperazino, dihydropyridino,and the like.

Unless otherwise constrained by the definition for the heterocyclylsubstituent, such heterocyclyl groups can be optionally substituted with1, 2, 3, 4 or 5, and typically 1, 2 or 3 substituents, selected from thegroup consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl,cycloalkenyl, acyl, acylamino, acyloxy, amino, aminocarbonyl,alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl,carboxy, carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio,thiol, alkylthio, aryl, aryloxy, heteroaryl, aminosulfonyl,aminocarbonylamino, heteroaryloxy, heterocyclyl, heterocyclooxy,hydroxyamino, alkoxyamino, nitro, —SO-alkyl, —SO-aryl, —SO-heteroaryl,—SO₂-alkyl, —SO₂-aryl and —SO₂-heteroaryl. Unless otherwise constrainedby the definition, all substituents may optionally be furthersubstituted by 1-3 substituents chosen from alkyl, carboxy,carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF₃, amino,substituted amino, cyano, and —S(O)_(n)R_(SO), where R_(SO) is alkyl,aryl, or heteroaryl and n is 0, 1 or 2.

The term “thiol” refers to the group —SH.

The term “substituted alkylthio” refers to the group —S-substitutedalkyl.

The term “heteroarylthiol” refers to the group —S-heteroaryl wherein theheteroaryl group is as defined above including optionally substitutedheteroaryl groups as also defined above.

The term “sulfoxide” refers to a group —S(O)R_(SO), in which R_(SO) isalkyl, aryl, or heteroaryl. “Substituted sulfoxide” refers to a group—S(O)R_(SO), in which R_(SO) is substituted alkyl, substituted aryl, orsubstituted heteroaryl, as defined herein.

The term “sulfone” refers to a group —S(O)₂R_(SO), in which R_(SO) isalkyl, aryl, or heteroaryl. “Substituted sulfone” refers to a group—S(O)₂R_(SO), in which R_(SO) is substituted alkyl, substituted aryl, orsubstituted heteroaryl, as defined herein.

The term “keto” refers to a group —C(O)—.

The term “thiocarbonyl” refers to a group —C(S)—.

The term “carboxy” refers to a group —C(O)OH.

The term “conjugated group” is defined as a linear, branched or cyclicgroup, or combination thereof, in which p-orbitals of the atoms withinthe group are connected via delocalization of electrons and wherein thestructure can be described as containing alternating single and doubleor triple bonds and may further contain lone pairs, radicals, orcarbenium ions. Conjugated cyclic groups may comprise both aromatic andnon-aromatic groups, and may comprise polycyclic or heterocyclic groups,such as diketopyrrolopyrrole. Ideally, conjugated groups are bound insuch a way as to continue the conjugation between the thiophene moietiesthey connect.

Disclosed are compounds, compositions, and components that can be usedfor, can be used in conjunction with, can be used in preparation for, orare products of the disclosed methods and compositions. These and othermaterials are disclosed herein, and it is understood that whencombinations, subsets, interactions, groups, etc. of these materials aredisclosed that while specific reference of each various individual andcollective combinations and permutation of these compounds may not beexplicitly disclosed, each is specifically contemplated and describedherein. Thus, if a class of molecules A, B, and C are disclosed as wellas a class of molecules D, E, and F and an example of a combinationmolecule, A-D is disclosed, then even if each is not individuallyrecited, each is individually and collectively contemplated. Thus, inthis example, each of the combinations A-E, A-F, B-D, B-E, B-F, C-D,C-E, and C-F are specifically contemplated and should be considereddisclosed from disclosure of A, B, and C; D, E, and F; and the examplecombination A-D. Likewise, any subset or combination of these is alsospecifically contemplated and disclosed. Thus, for example, thesub-group of A-E, B-F, and C-E are specifically contemplated and shouldbe considered disclosed from disclosure of A, B, and C; D, E, and F; andthe example combination A-D. This concept applies to all aspects of thisdisclosure including, but not limited to, steps in methods of making andusing the disclosed compositions. Thus, if there are a variety ofadditional steps that can be performed it is understood that each ofthese additional steps can be performed with any specific embodiment orcombination of embodiments of the disclosed methods, and that each suchcombination is specifically contemplated and should be considereddisclosed.

Embodiments comprise rationally designed compounds and polymerscomprising optionally-substituted dihydropyrroloindoles (“DHPI”),dipyrrolothiophenes or fused pyrroles (all generally referred to as“pyrrole groups” herein) bridged to optionally substituteddiketopyrrolopyrroles (“DPP”). The materials have advantages over DPPalone in that they are soluble in non-chlorinated solvents, efficientlysynthesized, and show very high mobilities in non-chlorinated solvents.Further, the compounds are relatively easy to modify and substituentscan be introduced to multiple positions which allows for fine tuningmaterial packing behaviors.

In one aspect, described herein are compositions comprising the formula1a, 1b, 1c, 1d, 1e, or 2:

wherein Ar is an optionally substituted aromatic or heteroaromatic groupor conjugated group; k is an integer from 0 to 5 with the proviso thatwhen k is 0, the structure results in a direct bond between thethiophene and pyrrole group; each X is independently NR₁, PR₁, AsR₁, Sb,O, S, Te, or Se, with the proviso that due to conjugation, X may bebonded to one or more additional R₁; each Y is independently H, halo,trialkylsilane, optionally substituted C₁-C₄₀ alkyl, optionallysubstituted aralkyl, alkoxy, alkylthio, optionally substituted C₂-C₄₀alkenyl, optionally substituted C₂-C₄₀ alkynyl, aminocarbonyl,acylamino, acyloxy, aryl, aryloxy, optionally substituted amino,carboxyalkyl, optionally substituted cycloalkyl, optionally substitutedcycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionallysubstituted heteroaralkyl, heteroaryloxy, optionally substitutedheterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substitutedsulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo,Sn(alkyl)₃, SnH₃, B(OH)₂, B(alkoxy)₂, or OTs; each R, R₁, R₂, and R₃ isindependently H, halo, optionally substituted C₁-C₄₀ alkyl, optionallysubstituted aralkyl, alkoxy, alkylthio, optionally substituted C₂-C₄₀alkenyl, optionally substituted C₂-C₄₀ alkynyl, aminocarbonyl,acylamino, acyloxy, optionally substituted aryl, aryloxy, optionallysubstituted amino, carboxyalkyl, optionally substituted cycloalkyl,optionally substituted cycloalkenyl, halo, acyl, optionally substitutedhetero aryl, optionally substituted heteroaralkyl, heteroaryloxy,optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol,optionally substituted sulfoxide, or optionally substituted sulfone.

In some embodiments, the compound comprises 1a or 1b. In otherembodiments, the compound comprises 1c or 1d, or 1e. In still otherembodiments, the compound comprises 2. In some embodiments, X is NR₁,PR₁, AsR₁, Sb, O, S, Se, or Te with the proviso that due to conjugation,X may be bonded to one or more additional R₁; and each R, R₁, R₂, and R₃is independently H, halo, optionally substituted C₁-C₄₀ alkyl,optionally substituted aralkyl, alkoxy, alkylthio, optionallysubstituted C₂-C₄₀ alkenyl, optionally substituted C₂-C₄₀ alkynyl,aminocarbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy,optionally substituted amino, carboxyalkyl, optionally substitutedcycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionallysubstituted heteroaryl, optionally substituted heteroaralkyl,heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio,heteroarylthiol, optionally substituted sulfoxide, or optionallysubstituted sulfone.

In some embodiments, each R, R₁, R₂, and R₃ is independently H,optionally substituted alkyl, halo, optionally substituted alkenyl,optionally substituted alkynyl, optionally substituted aryl, optionallysubstituted heteroaryl, optionally substituted heteroaralkyl, optionallysubstituted cycloalkyl, optionally substituted cycloalkenyl, optionallysubstituted heterocyclyl, or aralkyl.

In some embodiments, each R, R₁, R₂, and R₃ is independently H, halo,optionally substituted alkyl, optionally substituted alkenyl, optionallysubstituted alkynyl, optionally substituted cycloalkyl, optionallysubstituted cycloalkenyl, optionally substituted heterocyclyl, oroptionally substituted phenyl, optionally substituted thiophenyl,optionally substituted furanyl, optionally substituted pyrrolyl,optionally substituted imidazolyl, optionally substituted triazolyl,optionally substituted oxaxolyl, optionally substituted thiazolyl,optionally substituted napthalenyl, optionally substitutedisoquinolinyl, optionally substituted quinolinyl, or optionallysubstituted naphthyridinyl.

In some embodiments, each R₂ is independently H, optionally substitutedalkyl, or halo. In particular, due to improvements in solubility andother factor, it is advantageous in some embodiments to have at leastone or more of R, R₂, or R₃ independently be an optionally substitutedC₁-C₂₀ alkyl or C₂-C₂₀ alkenyl, and in particular an optionallysubstituted branched C₁-C₂₀ alkyl or C₂-C₂₀ alkenyl. Particularembodiments may have optionally substituted C₁-C₂₀ alkyl groups only onone or more R₂ groups, or alternatively only on one or more R groups.

In some embodiments, particularly where compounds 1a-1e and 2 are to beused in polymerization steps, each Y is independently H, halo,—OSO-alkyl, —Mg-halo, —Zn-halo, —Sn(alkyl)₃, —SnH₃, —B(OH)₂, or—B(alkoxy)₂.

Another aspect comprises methods of making compounds 1a-1e and 2. Theformation of the dipyrrolopyrole (DPP) moiety can be done via thereaction scheme shown in Tieke et al., Beilstein, J. Org. Chem. 830(2010), 25 Chem. Mater. 782 (2013), and U.S. application Ser. No.13/665,055, all of which are herein incorporated by reference in theirentireties. Generally, the reaction to form the DPP moiety is shown viathe following reaction scheme (Scheme 1):

Formation of the pyrrole groups can be done via a number of chemicalprocesses. For example, it can be done via cyclization of a diamine- oramide-modified benzene ring. A number of cyclization processes have beendeveloped to prepare the DHPIs described herein. For example, in Scheme2, a N,N′-1,4-Phenylenebis[2-chloro-N—R₂]acetamide is added to anhydrousaluminum chloride in an oil bath at ˜200° C., cooled and filtered toproduce the DHPI-dione shown.

The DHPI-dione can be converted to a di-halo moiety via reaction (Scheme3):

Similarly, PCl₅ can be used to make the chlorine-based equivalent of thestructure in Scheme 3.

The modification nitrogen on the diindole group can be accomplished viathe use of a base, such as potassium tert-butoxide (t-BuOK) in solvent(e.g., DMSO) followed by reaction with R₂Br (Scheme 4):

where R, R₁, Ar, X, and k are as noted above. These reactions can alsobe applied to the other compounds disclosed herein.

Dibromination of the pyrrole groups can be accomplished using techniquesdeveloped by the inventors, see, e.g., PCT Int. Appl., 2011146308,herein incorporated by reference in its entirety, where a compounds suchas N-bromosuccinimide is used to brominate the pyrrole groups throughradical reaction (Scheme 5):

Likewise, precursors to compounds 1b-1e, and 2, may also be brominatedin a similar fashion.

In some cases, it is advantageous to place a reactive tin group on thepyrrole groups. It is possible to obtain a ditin-modified pyrrole groupvia methods developed by the inventors, see, e.g., U.S. Pat. No.8,278,346, herein incorporated by reference in its entirety. The ditincompound may be obtained either directly from reaction of a di-hydrogencompound or from the dibromo compound as shown in Scheme 6:

Likewise, the pyrrole groups in 1b-1e, and 2, may also be converted in asimilar fashion.

In some embodiments, it may be advantageous to create a monomer of 1a-1eor 2. In such cases, it may be necessary to modify the chemistry ofScheme 6 to limit the formation of the ditin group to one side of thepyrrole compound. Modifications including the use of protecting groupsor rendering reactive sites inactive is known in the art. Once the tincompound is formed, the pyrrole compound may be reacted with abromo-modified DPP to produce compounds 1a-1e and 2. For example, atin-modified compound of structure:

is reacted with a di-halo DPP of structure:

where X is halo and Ar, k, R, R₁, R₂, and R₃ are as defined above toproduce structure 1a. This reaction is equally applicable to the otherpyrrole structures in 1b-1e and 2.

In another aspect, the composition comprises a polymer comprising atleast one moiety of formula 1a′, 1b′, 1c′, 1d′, 1e′, or 2′:

wherein n is an integer greater than zero; X, Y, R, R₁, and R₂ all havethe same meanings as above. In some embodiments, n is an integer fromabout 1 to 500. In some embodiments, n is an integer from about 3 toabout 20, about 3 to about 15, about 3 to about 12, about 3 to about 10,or about 5 to about 9. In some embodiments, n is an integer about 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 30, 40,50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, or 500.

Another aspect comprises a method of making a polymer comprising atleast one moiety of formula 1a′, 1b′, 1c′, 1d′, 1e′, or 2′:

by respectively polymerizing a compound of structure:

with a compound of structure:

where X is halo and Z is H or an optionally substituted alkyl and n, X,Y, R, R₁, and R₂ all have the same meanings as above.

The polymerization may be done via a method similar to that shown inU.S. Pat. No. 8,278,346, herein incorporated by reference in itsentirety. For example, a ditin compound of structure:

where is reacted with a di-halo DPP of structure:

where X is halo and Ar, k, R, R₁, R₂, and R₃ are as defined above. Thisreaction is equally applicable to the other pyrrole structures of 1b-1eand 2.

Alternatively, in some embodiments, it may be possible to form thepolymers directly from compounds 1a-1e and 2. For example, suchembodiments may be made by forming two solutions of compounds 1a-1e and2 with different reactive groups, for example where for one solution Yis a ditin moiety, and for a second solution Y is a dibromo moiety. Uponcombination and reaction of the two solutions, polymerization leading toa polymer of 1a′-1e′ or 2′ would result.

In another aspect, embodiments herein are optimized for reorganizationenergy and mobility. In some embodiments, compounds embodied herein haveimproved solid state properties as a result of lower reorganizationenergy and/or higher mobility. In some embodiments, the properties ofthe compounds embodied herein may be described by Marcus theory (R. A.Marcus, 65 REV. MOD. PHYS. 599 (1993), herein incorporated by referencein its entirety).

Charge transport properties depend critically on the degree of orderingof the system or molecular ordering in the solid state, as well as thedensity of chemical impurities and/or structural defects such as grainsize and dislocations. At the electronic level, two of the mostimportant factors that control transport properties in organicconjugated materials are the interchain transfer integral β, and thereorganization energy λ. The transfer integral expresses the ease oftransfer of a charge between interacting chains. The reorganizationenergy term describes the strength of the electron-phonon coupling. Itis proportional to the geometric relaxation energy of the chargedmolecule over the individual neutral unit. In the context ofsemi-classical electron-transfer theory, the electron-transfer (hopping)rate can be expressed from Marcus theory in a simplified way as:

$\begin{matrix}{k_{et} = {\frac{4\pi^{2}}{h}\frac{1}{\sqrt{4\pi \; k_{B}\lambda \; T}}\beta^{2}^{- \frac{\lambda}{4k_{B}T}}}} & (1)\end{matrix}$

(R. A. Marcus, 65 REV. MOD. PHYS. 599 (1993), herein incorporated byreference in its entirety) where T is the temperature, λ is thereorganization energy, β is the transfer integral, and h and k_(B) arethe Planck and Boltzmann constants, respectively.

It is possible to simplify equation (1) to:

$\begin{matrix}{k_{et}^{simple} = {\frac{1}{\sqrt{\lambda}}\beta^{2}^{- \lambda}}} & (2)\end{matrix}$

in order to characterize the relative influence of both parameters λ andβ to the charge transport rate. As can be seen from equation (2), thedifference in mobility for different transfer integrals, β, is onlysignificant for small values of the reorganization energy, λ. A bigincrease in the transfer integral does not yield a significant variationin the mobility, unless the reorganization energies are small. Thisimplies that any optimization of the mobility should start with thedesign of single molecules with very low reorganization energy.

The reorganization energy includes two contributions that are associatedwith charge hopping. One is introduced by the geometric changes withinthe single molecule, and is denoted the internal part. The second onearises from the repolarization changes of the surrounding medium and isusually much smaller than the first one. In studies to qualitativelyorder molecules, it is generally valid to neglect this last contributionin the evaluation of the reorganization energy as no significant solventreorganization occurs during the charge transfer in the condensed phase.

Table 1 incorporates reorganization energies for a number ofembodiments. For each molecule, the geometry is optimized using quantummechanics for both neutral and ionic states. Consequently, the basichopping step in a molecular wire is defined by four energies: E₀ and E₊represent the energies of the neutral and cation species in their lowestenergy geometries, respectively, while E₀* and E₊* represent theenergies of the neutral and cation species with the geometries of thecation and neutral species, respectively. The table provides neutraltotal dipole for the molecule, the vertical ionization potential, thehole reorganization energy, and the Pareto Front.

The quantum mechanics calculations to determine these above mentionedquantities used the experimentally parameterized Hamiltonian PM6implemented in VAMP® semi-empirical molecular orbital software (AccelrysSoftware Inc.). Pentacene was used as the reference to validate the HoleReorganization Energy calculations. Experimental data for Pentacene REwas ˜0.12 eV (see M. Malagoli and J. L. Bredas, 327 CHEM. PHYS. LETT. 13(2000) and N. W. Gruhn et al., 89 PHYS. REV. LETT. 275503 (2002), bothhereby incorporated by reference in their entirety), compared to 0.114eV from our calculations based on VAMP® (Accelrys Software Inc.).

Hole Reorganization energies for embodiments may comprise from about 0eV to about 0.75 eV. In some embodiments, the hole reorganization energyis from about 0.04 to about 0.75 eV. In some embodiments, the holereorganization energy is 0.75 eV or less. In some embodiments, the holereorganization energy is about 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10,0.11, 0.12, 0.13, 0.14, 0.15, 0.17, 0.19, 0.20, 0.22, 0.25, 0.27, 0.30,0.31, 0.32, 0.33, 0.34, 0.35, 0.37, 0.40, 0.45, 0.50, 0.60, 0.70, or0.75.

TABLE 1 Neutral Total Dipole Vertical Hole Reorg Pareto Compound [D] IP[eV] Energy [eV] Front

5.1790 6.6477 0.084295 1

5.2820 6.9662 0.089012 2

3.1940 6.8983 0.099444 3

3.0520 6.8904 0.10484 4

6.8030 6.7374 0.10872 5

3.0230 7.2784 0.11478 6

0.012000 7.7531 0.11516 7

6.2260 6.5287 0.12915 8

3.2690 6.5633 0.12955 9

4.4890 6.7172 0.13477 10

5.5240 6.9820 0.13575 11

1.6100 7.0450 0.14477 12

5.0320 6.5885 0.15718 13

7.9940 6.6464 0.16841 14

5.3830 6.6361 0.17426 15

6.4620 6.7225 0.19448 16

6.6250 6.5706 0.20366 17

5.5870 6.6298 0.24781 18

3.6340 6.9565 0.32312 19

3.9920 7.0522 0.33319 20

4.7780 6.7736 0.33917 21

5.5350 7.1914 0.33931 22

5.0060 6.7713 0.35348 23

5.1560 6.8570 0.36994 24

6.7190 6.8271 0.37773 25

7.8630 7.1224 0.63376 26

4.6680 7.7050 0.67130 27

The compositions described herein (monomers, oligomers, polymers) can beused to make a wide variety of devices. For example, the device can be afused thiophene moiety-containing composition configured in anelectronic, optoelectronic, or nonlinear optical device. Thecompositions described herein can also be used in field effecttransistors (FETs), thin-film transistors (TFTs), organic light-emittingdiodes (OLEDs), PLED applications, electro-optic (EO) applications, asconductive materials, as two photon mixing materials, as organicsemiconductors, as non-linear optical (NLO) materials, as RFID tags, aselectroluminescent devices in flat panel displays, in photovoltaicdevices, and as chemical or biological sensors.

The polymers comprising the fused thiophene moieties described herein(1a′, 1b′, 1c′, 1d′, 1e′, and 2′) possess several advantages oversimilar compounds. The polymers embodied herein are easier to modify onthe designed fused rings, allowing for improvements in thepolymerization process and processibility. Further, substituents can beintroduced to multiple positions which can enable fine tuning materialpacking behaviors.

EXAMPLES

The methods disclosed herein are intended for purposes of exemplifyingonly and are not to be construed as limitations thereon. Those skilledin the art will appreciate that other synthetic routes may be used tosynthesize the inventive compounds. Some aspects of some embodiments maybe synthesized by synthetic routes that include processes analogous tothose well-known in the chemical arts, particularly in light of thedescription contained herein. Although specific starting materials andreagents are depicted in the schemes and discussed below, other startingmaterials and reagents can be easily substituted to provide a variety ofderivatives and/or reaction conditions. The starting materials aregenerally available from commercial sources, such as Aldrich Chemicals(Milwaukee, Wis.), or are readily prepared using methods well known tothose skilled in the art (e.g., prepared by methods generally describedin Louis F. Fieser and Mary Fieser, REAGENTS FOR ORGANIC SYNTHESIS, v.1-19, Wiley, New York (1967-1999 ed.), or BEILSTEINS HANDBUCH DERORGANISCHEN CHEMIE, 4, Aufl. ed. Springer-Verlag, Berlin, includingsupplements (also available via the Beilstein online database)). Inaddition, many of the compounds prepared by the methods described belowcan be further modified in light of this disclosure using conventionalchemistry well known to those skilled in the art.

The following examples are put forth so as to provide those of ordinaryskill in the art with a complete disclosure and description of how thematerials, articles, and methods described and claimed herein are madeand evaluated, and are intended to be purely exemplary and are notintended to limit the scope. Efforts have been made to ensure accuracywith respect to numbers (e.g., amounts, temperature, etc.) but someerrors and deviations should be accounted for. Unless indicatedotherwise, parts are parts by weight, temperature is in ° C. or is atambient temperature, and pressure is at or near atmospheric. There arenumerous variations and combinations of reaction conditions, e.g.,component concentrations, desired solvents, solvent mixtures,temperatures, pressures and other reaction ranges and conditions thatcan be used to optimize the product purity and yield obtained from thedescribed process. Although specific starting materials and reagents aredepicted in the Examples below, other starting materials and reagentscan be easily substituted to provide a variety of derivatives and/orreaction conditions. In addition, many of the compounds prepared by themethods described below can be further modified in light of thisdisclosure using conventional chemistry well known to those skilled inthe art. Only reasonable and routine experimentation will be required tooptimize such process conditions.

Example 1

N,N′-Didecahexylbenzene-1,4-diamine (1)—Cyclohexa-1,4-dione (6 g, 53.5mmol) dissolved in 10 ethanol at 50° C. is added to a solution ofhexdecylamine 28.4 g (technical grade) in ethanol (500 ml) in a beaker.The solution is vigorously stirred for 2 h and the resulting suspensionis filtered and washed twice with 50 mL of hot ethanol. The yield of thetan powder is 15.7 g (53%). ¹H NMR (400 MHz, Chloroform-d) δ 6.54 (s,4H), 3.02 (t, J=7.1 Hz, 4H), 1.57 (p, J=7.1 Hz, 4H), 1.39-1.24 (m, 52H),0.92-0.82 (m, 6H); ¹³C NMR (101 MHz, CDCl₃) δ 140.91, 114.72, 45.0,31.91, 29.77, 29.67, 29.60, 22.68, 14.11.

Example 2

N,N′-1,4-Phenylenebis[2-chloro-N-hexyl]acetamide (2)—A solution of 1 (10g, 17.95 mmol) and 4-(dimethylamino)pyridine (DMAP) (4.39 g, 35.11 mmol)in THF (500 mL) is added drop wise to a solution of chloroacetylchloride (6.08 g, 53.86 mmol) in THF (100 mL) at 0° C. After 1 h, thereaction mixture is concentrated to about 50 mL and quenched with water.The precipitate is collected by filtration. After being washed withwater and methanol, the solid is dried in vacuo to yield 8.4 g (65%). ¹HNMR (400 MHz, CDCl₃) δ 7.30 (s, 4H), 3.80 (s, 4H), 3.74-3.63 (m, 4H),1.71 (m, 4H), 1.51 (d, J=7.6 Hz, 4H), 1.22 (m, J=4.3 Hz, 16H), 0.85 (t,J=6.7 Hz, 48H); ¹³C NMR (101 MHz, CDCl₃) δ 165.4, 140.35, 126.32, 51.56,41.72, 31.89, 29.66, 29.63, 29.61, 29.55, 29.33, 29.27, 26.66, 22.89,22.66, 14.10.

Example 3

1,5-dihexadecyl-5,7-dihydropyrrolo[2,3-f]indole-2,6(1H,3H)-dione (3)—940mg of anhydrous aluminum chloride is added to 1 g of 2. The mixture ispaced in an oil bath at 190° C. for 1 h. After cooling, cracked ice isadded to quench the reaction. The precipitate formed is collected byfiltration. After being washed with water and methanol, the solid isdried and further purified by column chromatography on silica gel withDCM:ethyl acetate=10:1 as eluent to yield 3 (56 mg, 6%) as a brownsolid. ¹H NMR (400 MHz, CDCl₃) δ 6.75 (s, 4H), 3.60 (s, 4H), 1.82 (d,J=7.6 Hz, 4H), 1.22 (m, 16H), 0.86 (t, J=6.7 Hz, 48H); ¹³C NMR (101 MHz,CDCl₃) δ 175.4, 140.00, 123.32, 105.6 35.90, 31.89, 29.66, 29.63, 29.61,29.55, 29.33, 29.81, 26.67, 22.89, 22.56, 14.10.

Example 4

A solution of 1 (0.2 g), t-NaOBu (0.22 g), Pd₂dba₃ (44 mg) and s-BINAP(120 mg) in dry toluene (6 mL) is purged with nitrogen for 20 min.NH₂C₅H₁₁ (0.9 mL) is added via a syringe and the mixture is stirredunder nitrogen at 110° C. for 30 min. After cooling to room temperature,water is added to the solution and the reaction mixture is extractedtwice with diethyl ether. After the organic phases are dried over MgSO₄,the solvents are removed using a rotary evaporator. The crude product ispurified by column chromatography and the desired product (4) isobtained as white solid (MS found=MS calculated=406).

Example 5

(4) (116 mg) is mixed with CuI (3 mg), Pd(PPh₃)₂Cl₂ and TEA (6 mL) in anoven dried flask under Ar. The solution is degassed for 2-5 min.TMS-acetylene (0.4 mL) is added and the reaction mixture is stirred at90° C. for 3.5 h. After cooling down to room temperature, the reactionmixture is filtered through celite, the solid residue is washed withEtOAc, and the combined organic phases are concentrated under reducedpressure. Flash column chromatography yields the desired targetstructure (5) (MS found=MS calculated=440).

Example 6

TBAF is added to a solution of (5) (about 100 mg) in THF (2 mL) at 0° C.and the resulting solution is stirred for 30 min. H₂O is added to dilutethe solution, and then the organic layer is separated, washed withbrine, and dried over Na₂SO₄. The solvent is removed under reducedpressure and the residue is purified by silica gel column chromatographyto afford (6) as major compounds along with (7) as a minor compound (MSfound=MS calculated=296).

Example 7

In a pressure tube, to a solution of (6) (contaminated small amount of(7)) (about 100 mg of (6) & (7)) in DMSO (3 mL), is added 110 mg ofcrushed KOH. The reaction is stirred at 120° C. overnight to convert all(6) into (7). The reaction is brought to room temperature and thereaction mixture is extracted through ethyl acetate-water partitioning.Ethyl acetate is dried over MgSO₄ and evaporated under reduced pressure(MS found=MS calculated=296).

Example 8

The addition of non-hydrogen R-groups to the nitrogen on the pyrrolegroup, for example, a commercially available, unmodified diindole, canbe done via use of a base such as t-BuOK in DMSO with subsequentreaction with an alkyl bromide:

This reaction is based on work shown in references 34 New J. Chem. 1243(2010) and 213 Macro. Chem. Phys. 425 (2012), herein incorporated byreference in their entireties.

Example 9

The compound formed in Example 8 can be reacted with N-butylsuccinimideto form the brominated diindole:

based on the teaching shown in PCT Publ. No. 2011/146308 (2011), hereinincorporated by reference.

Example 10

The compound formed in Example can be reacted with n-BuLi in THF orhexane and then a tin complex for form the ditin diindole:

based on the teaching shown in U.S. Pat. No. 8,278,346, hereinincorporated by reference.

What is claimed is:
 1. A compound of formula:

wherein Ar is an optionally substituted aromatic or heteroaromatic groupor conjugated group; k is an integer from 0 to 5 with the proviso thatwhen k is 0, the structure results in a direct bond between thethiophene and pyrrole group; each X is independently NR₁, PR₁, AsR₁, Sb,O, S, Te, or Se, with the proviso that due to conjugation, X may bebonded to one or more additional R₁; each Y is independently H, halo,trialkylsilane, optionally substituted C₁-C₄₀ alkyl, optionallysubstituted aralkyl, alkoxy, alkylthio, optionally substituted C₂-C₄₀alkenyl, optionally substituted C₂-C₄₀ alkynyl, aminocarbonyl,acylamino, acyloxy, aryl, aryloxy, optionally substituted amino,carboxyalkyl, optionally substituted cycloalkyl, optionally substitutedcycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionallysubstituted heteroaralkyl, heteroaryloxy, optionally substitutedheterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substitutedsulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo,Sn(alkyl)₃, SnH₃, B(OH)₂, B(alkoxy)₂, or OTs; and each R, R₁, R₂, and R₃is independently H, halo, optionally substituted C₁-C₄₀ alkyl,optionally substituted aralkyl, alkoxy, alkylthio, optionallysubstituted C₂-C₄₀ alkenyl, optionally substituted C₂-C₄₀ alkynyl,aminocarbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy,optionally substituted amino, carboxyalkyl, optionally substitutedcycloalkyl, optionally substituted cycloalkenyl, acyl, optionallysubstituted heteroaryl, optionally substituted heteroaralkyl,heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio,heteroarylthiol, optionally substituted sulfoxide, or optionallysubstituted sulfone.
 2. The compound of claim 1, wherein the compoundcomprises structure 1a or 1b.
 3. The compound of claim 1, wherein thecompound comprises structure 1c, 1d, or 1e.
 4. The compound of claim 1,wherein the compound comprises structure
 2. 5. The compound of claim 1,wherein k is from 0-3.
 6. The compound of claim 5, wherein k is
 0. 7.The compound of claim 1, wherein Ar is an optionally substituted aryl orheteroaryl.
 8. The compound of claim 1, wherein Ar is a thiophene orfused thiophene.
 9. The compound of claim 8, wherein the thiophene orfused thiophene is bonded to compound via the α positions and optionallysubstituted with one or more C₁-C₂₀ alkyl groups at the β positions. 10.The compound of claim 1, wherein X is N, S, or O.
 11. The compound ofclaim 1, wherein Y is H, optionally substituted alkyl, or halo.
 12. Thecompound of claim 1, wherein each R₁ and R₃ are independently H,optionally substituted alkyl, halo, optionally substituted alkoxy,optionally substituted alkylthiol, or optionally substituted alkenyl.13. The compound of claim 12, wherein each R and R₂ are independently H,optionally substituted alkyl, halo, or optionally substituted alkoxy.14. A method of making a compound of claim 1, the method comprisingreacting a compound of structure:

with a compound of structure:

where X is halo and Z is H or an optionally substituted alkyl.
 15. Themethod of claim 14, wherein k is from 0-3.
 16. The method of claim 14,wherein Ar is an optionally substituted aryl or heteroaryl.
 17. Themethod of claim 1, wherein X is N, S, or O.
 18. The method of claim 1,wherein each R₁ and R₃ are independently H, optionally substitutedalkyl, halo, optionally substituted alkoxy, optionally substitutedalkylthiol, or optionally substituted alkenyl.
 19. The method of claim18, wherein each R and R₂ are independently H, optionally substitutedalkyl, halo, or optionally substituted alkoxy.
 20. The method of claim14, wherein k is from 0-3, Ar is a thiophene or fused thiophene, X is N,S, or O, Y is H, optionally substituted alkyl, or halo, and each R₁ andR₃ are independently H, optionally substituted alkyl, halo, optionallysubstituted alkoxy, optionally substituted alkylthiol, or optionallysubstituted alkenyl.